Method of treating hydrocarbons with a double-function catalyst



Jan. 19, 1954 B MOCONNELL 2,666,732

METHOD OF TREATING HYDROCARBONS WITH A DOUBLE-FUNCTION CATALYST Filed Feb. 12, 1949 2 Sheets-Sheet 2 A1: ATTORNEYS.

UNITED STATES PATENT OFFICE LIETHOD OF TREATING HYDROCARBONS WITH A DOUBLE-FUNCTION CATALYST Elliott B. McConnell, Shaker Heights, Ohio, assignor to The Standard Oil Company, Cleveland, Ohio, a corporation of Ohio Application February 12, 1949, Serial No. 76,104

4 Claims. (Cl. 196-52) catalytic cracking processes that may, if desired,

be widely spaced in time and distance, wherein the regenerator for the cracking catalyst is utilized not only to regenerate the catalyst but also to regenerate the adsorbent contact material for further use in either or both the contact or cracking operations.

It has been known that it ispcssible to burn off spent contact clay but it has, to the best of my knowledge, been considered necessary to conduct such an operation in a furnace constructed for that purpose. This practice is generally not deemed economical, however, because the initial and maintenance costs of such a furnace are not warranted in view of the low cost of contact clays. In accordance with my invention, the regenerator of a catalytic cracking unit is used to regenerate the spent contact material. method is economical because the regeneration can be carried out without necessitating equipment.

To cite an illustrative example without, however, intending to limit the scope of this invention thereto, the principles of this invention may be applied to the decolorization of lubricating additional .oils and to the cracking of hydrocarbons to form ing oils with adsorbent contact material has no deleterious efiect upon the ability of the material to be regenerated in a regenerator normally used solely to regenerate catalytic material used in a catalytic cracking operation and that such regenerated contact material is substantially v equally suitable for further use in either an adsorption or cracking operation.

The present invention, therefore, contemplates a method wherein spent contact material from an adsorption process and catalyst from a catalytic cracking operation may both be regenerated in a given regenerating unit. The material utilized in the adsorption process may be the same or different from that used in the cracking operation, depending upon the requirements dej scribed more fully hereinafter.

. material is utilized as catalyst in the catalytic cracking reactor and in th lube oil contact plant, the material leaving the reactor and the contact plant being regenerated in a common regenerator and recycled to the reactor and contact P In another embodiment, where the adsorption material and catalyst are different materials, the spent contact material and used catalyst'are regenerated cyclically in a common regenerator. In this embodiment, the contajctpl'ant is run continuously on contact material'and' the cracking reactor is run cyclically on catalyst and contact material.

One of the advantages of'this invention is that it provides a simple and economical means for regenerating contact materials known primarily for their adsorbent properties. Another advanta'ge of the invention is that the regenerating casolely for the regeneration of spent catalyst from 'a cracking operation, may be utilized more fully h it makes possible appreciable economies in the and that spent contact material hitherto uneconomical to regenerate may now be regenerated without the addition of more equipment.

' Another advantage of the invention is that it maybe utilized for the treatment of any lubricating oil whether it be unrefined, solvent treated or acid treated.

Still another advantage of the invention is that operation of both.

The contact material employed in the method of this invention may be any material known to have adsorptive as well as catalytic properties. The preferred material includes the silica-alumina type catalysts commonly referred to as contact clays, such as members of the group of acidactivated, natural clays made from the mineral montmorillonite, available from the Filtrol Corporation and marketed under. trade names such as Filtrol and Super Filtrol lube contact clays as well as fluid catalysts of the natural clay type available under the trade name Filtrol D and fluid catalysts made synthetically by precipitating alumina and silica, which are available as the spray-dried and oil dropped Microsphere type and Diakell catalysts available from The Universal Oil Products Company and a contact plant, cracking plant, or

M.- W. Kellogg Company, respectively.

The various embodiments of the invention are further described in the following examples made with reference to the accompanying drawing wherein: v

Figure 1 is a diagrammatic flow sheet; and

Figure 2 is a flow sheetlllustrating, one preregenerated contact'play ig'rom stor 9 'fresh make-upclay from source {2. m

: contact clay;xby;the fmler utilize op ferred embodiment of the method or this invention.

EXAMPLE 1 When the operation of the cracking unit is such that a fluid type catalyst is required, one method of procedure, which is herein described with reference to Figure 1, is to operate both a catalytic cracking reactor l and a lube oil con-- tact plant H on the fluidcatalystythemake-up requirements being obtained fromgaisource 1,4. In this embodiment, the stream I6, I] of fluid catalyst from catalytic cracking unit is coinbined with a stream [9, ofcatalyst from the contact plant ll into a single stream 2!. The combined stream 2| of catalyst then-enters re;- generator 22 and the regenerated catalyst leaves the regenerator in the form of a single stream 2 1, which is divided into two streams .26 and 2'5 for recycling tofthe catalytic cracking unit {0 and the contact plant! I. Themakefup catalyst required passesdire'ctly from source i 4 into the cracking unit It in the form bf a stream 29, '30.

, The advantage er this type at eperanen is that the regenerator 22 is made available for regeneration of the catalyst used as adsorbent in the contact plant as we'll'as' for theregenerationof the catalyst coming iron; the catalytic cracking reactor without in anyway interfering with theoperation optimum conditions.

' EXAMPLE 2 ,7 When it is desired to operate the catalytic cracking reactor, for at least part of the time,

with fluid catalyst and it i's'preferred to operate the contact plant with a' contact clay, as might well be the case when the contact plant j and the cracking unit are at a considerable distance from one another, the systemis operated cyclilc'all'y.

In one cycle, a stream "5, I'|',2 l of catalyst .from cracking reactor I0 is led to the regeneraltojr 2 2. The'regene'rate'd catalyst isthen' recycled to the catalytic crackingre'actor ID in the form of a stream 24; 3|, 32, 29, *and by way of regenerated catalyst storage 34, maker-up catalyst being supplied to the cracking reactor from source l4 inthe form of a stream 29, 30.

In the meantime, the lube oil contact plant 1H operates on contact clay and a stream v19; 36 of spent contact clayf'rom the contact plant is led to a spent clay storage zone 31; e

When'th'e' storage zone 31 has been filled, the spent clay is directed into regenerator. 22 inthe :form of a stream 39;'2|. The regenerated contact clay is then "recycled to contact plant H ;in

*theform of a Jstream24, 21, 40; to; the cracking reactor'll in'the form of a stream 24,26, 30, and the excess regenerated clay 'is passedgto regenerated contact clay storage 4| pin the form of a stream 24, 42. Ariyfresh contact clay required the form-of a stream 44,140... When the spent "clay storage 3'! has :been substantially emptied,

This method of procedure has/6.1 .5; adv

peculiar toittot permitting regenerat generator 22 and without of the cracking reactor under preciable equipment. It is applicable whether the cracking reactor and the contact plant be in approximately the same physical location or at widely separated points. Furthermore, it has the advantage or reducing the overall volume of fluid catalyst circulating in the system inasmuch as none of it is circulated through the contact plant system.

EXAMPLE 3 Where the requirements of the catalytic crack.- ing reactor are not such as to require fluid catalyst but can be {satisfied by use of contact clay alone, the method of procedure is essentially similar to that of Example 1 except that the supply of make-up .clay may be varied.

Thus, for example, fresh contact clay, from source '12 and in amounts sufficient to supply the make-up requirements, may be added to either the contact plant II in the form of a stream 44, 40 or directly to the catalytic cracking reactor ill in the form of a stream M, 45, 30, or to both the contact plant and the cracking reactor. H

This procedure and the variations thereof referred to has the advantage of utilizing to the fullest the regenerating capacity of the regenerator 22.

Referring now to Figure 2 of the drawing, there is illustrated a preferred embodiment of the invention distinguished by the fact that the regnerator is utilized continuously to regenerate the contact material from both a cracking reactor'a'nd' an adsorption plant for decolorizing raw,

; solvent refined or acid treated oil.

'for make-up may be supplied from source I 2 in tank Stand from there In this embodiment, a portion of the oil from 'stcrage tanks 55 is passed by means of pump 5! through a heat exchanger 52 d rectly to a heater S t-arid another pcrtion is passed to the heater 5 by wayere mixing tank 5%. Contact material from a hopper ii? is introduced into the mixing passed into the heater 5% withtlie second portion of the oil to be treated. The heated mixture leaves the heater 5% by way or line 59 passes through the heat exchanger 52 and reduced into'a t me tank 60 to allow a prede ermined time of contact between the contact material the oil. From the time tank Ed the mixture is'passed into a rotary filter (it from whence the iiltrate passes into a filtrate receiver trend ultimately to a receiver for filtered oil. The spent contact material leaves the rotary filter "6 l by-way of lineii Lpasses through a receiver 66 andis purnped into the regenerator 61 together with material from the reactor 63. I The gaseous efliuentsfrom the regenerator iii are passed through a separator indicated schematicallyat 69. As in conventional practice, the regenerated Contact material leaves the regenerat'o'rdi byway of line l0. A portion of the relin {it and recycled to the hopper W for further use in the contact plant.

The oillcharge to be subjected to catalytic A crackingds passed through a charge preheater TI and introduced by way of line 72 into the reactorji'ttogether with the regenerated contact material remaining in linel'fi, The material from the reactor 68 leavesat'i i and. is recycled by the steamer a blower It and together with the spent contact material from the contact plant through line Tlto the regeherator 51.

As in conventionalpractice, the reaction prod- :iictsfidih reactor 58 leave the reactor at the top by way'or a separator .18 and line 19 and I *Imhass into a fractionator'iill wherein they are resolved into fractions of gas and gasoline, furnace oil, gas oil and a slurry that is recycled to the reactor 68 by way of thickener 8i and line 72.

Contact material in amounts sufficient tosatisfy the make-up requirements may be introduced into the system at any desirable point such as at 82 or 84. I

Tests have revealed that the catalytic activity, as determined by the standard Cat A test, of commercially available lubricating oil contact clay is 30 or over, and therefore sufiicient to be 7 used as a make-up catalyst to a fluid catalytic cracking unit. A comparison of the catalyt'c activity of one typical lubricating oil contact clay with two high activity fluid catalysts is given in Table 1 below:

TABLE 1 Catalytic activity of various lube oil contact clays and fluid catalysts Experiment Cat A No. Material activity 16891-93".-. Filtrol" lube contact clay (X417) 33. 1 1692729 Kellogg Diakcll fluid catalyst 40. 7 16931-33..." Filtrol grade D fluid catalyst 41. 5

TABLE 2 Optical density Material 5lbs./bbl. 10 lbs./bbl. 15lbs.lbbl. (1.5 weight (3.0 weight (4.5 weight percent) percent) percent) "Super Filtrol lube contact clay 159. 127. 3 111.5 Filtrol lube contact clay X 203.0 144.0 93.0 Kellogg Diakell fluid catalyst 147. 2 146. 0 89. 0 Filtrol grade D fluid catalyst 148. 0 110. 3 88. 2 U. 0. P. spray dried Microspheres" fluid catalyst 154. 0 114. 2 120. 5 U. 0. P. oil dropped Microspheres" 178. 2 203. 0 144. 0

Tests have been made to compare the effectiveness, as a lubricating oil contact clay, of a regenerated catalyst from a cracking operation and have shown that the adsorbing ability thereof is not materially afiected thereby. Thus, for example, the optical density of 1000 grams of solvent extracted bright stock, having a viscosity of 120 SUS at 210 F. and treated'for thirty minutes at 450 F. with lbs. per barrel of regenerated Kellogg Diakell fluid catalyst, was 153 whereas the optical density of a similar amount of the same oil treated in the same manner with fresh Kellogg Diakell fluid catalyst was 146. r

The catalystactivity was determined by the standard Cat-fl procedure and the materials used for clay contacting were blown dry with air prior to running the f Cat A tests.

The term optical density in the present disclosure represents the standard logarithmic ratio of intensity of an incident ray falling on a transparent or translucent medium to the intensity of the transmitted ray for a sample length of one meter and light of wave length from 5100 to 5500 Angstroms.

It is to be understood that innumerable variations and modifications will immediately become apparent to those skilled in the art upon reading the foregoing disclosure. The invention contemplates all such variations and modifications as come within the scope of the appended claims.

I claim:

1. A method of treating hydrocarbons which comp-rises contacting a lubricating oil in the liquid phase in a contact zone with a first stream of adsorbent silica-alumina contact catalytic material having both adsorbent and catalytic cracking properties and being in finely divided powder form for decolorizing said lubricating oil, crack ing hydrocarbons in a fluid catalytic cracking zone by contact with a second stream of adsorbent silica-alumina contact catalytic material likewise having both adsorbent and catalytic cracking properties and being in a finely divided powder form, passing all of the silica-alumina contact catalytic material in said first and second streams from said contact and cracking zones, respectively, directly into and through a fluidized regeneration zone for regeneration of the adsorbent and catalytic properties of the contact catalytic material in both said streams, recycling one portion of said regenerated contact catalytic material directly to the contact zone, and recycling the remainder of said regenerated contact catalytic material direcly to the fluid catalytic cracking zone.

2. The method defined in claim 1 in which the contact catalytic material in the first and second streams and the material regenerated in the fluidized regeneration zone is a synthetic silicaalumina fluid catalyst.

3. The method defined in claim 1 in which the contact catalytic material in the first and second streams and the material regenerated in the fluidized regeneration zone is a natural silicaalumina contact clay.

4. The method defined in claim 1 in which the contact catalytic material in the first stream and said one portion of regenerated contact catalytic material recycled to the contact zone is a silicaalumina contact clay and the contact catalytic material in the second stream and said reminder of the regenerated contact catalytic material recycled to the fluid catalytic cracking zone is a silica-alumina fluid catalyst.

ELLIOTT B. MCCONNELL.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,091,892 Stratford Aug. 31, 1937 2,227,416 Payne Dec. 31, 1940 2,286,654 Simpson et a1. June 16, 1942 2,361,978 Swearingen Nov. 7, 1944 2,409,234 Arveson Oct. 15, 1946 2,410,436 Ewing Nov. 5, 1946 2,426,903 Sweeney Sept. 2, 1947 2,450,724 Grote Oct. 5, 1948 2,464,127 Gary Mar. 8, 1949 2,549,518 Perry Apr..17, 1951 

1. A METHOD OF TREATING HYDROCARBONS WHICH COMPRISES CONTACTING A LUBRICATING OIL IN THE LIQUID PHASE IN A CONTACT ZONE WITH A FIRST STEAM OF ADSORBENT SILICA-ALUMINA CONTACT CATALYTIC MATERIAL HAVING BOTH ADSORBENT AND CATALYTIC CRACKING PROPERTIES AND BEING IN FINELY DIVIDED POWDER FORM FOR DECOLORIZING SAID LUBRICATING OIL, CRACKING HYDROCARBONS IN A FLUID CATALYTIC CRACKING ZONE BY CONTACT WITH A SECOND STREAM OF ADSORBENT SILICA-ALUMINA CONTACT CATALYTIC MATERIAL LIKEWISE HAVING BOTH ADSORBENT AND CATALYTIC CRACKING PROPERTIES AND BEING IN A FINELY DIVIDED POWDER FORM, PASSING ALL OF THE SILICA-ALUMINA CONTACT CATALYTIC MATERIAL IN SAID FIRST AND SECOND STREAMS FROM SAID CONTACT AND CRACKING ZONES, RESPECTIVELY, DIRECTLY INTO AND THROUGH A FLUIDIZED REGENERATION ZONE FOR REGENERATION OF THE ADSORBENT AND CATALYTIC PROPERTIES OF THE CONTACT CATALYTIC MATERIAL IN BOTH SAID STREAMS, RECYCLING ONE PORTION OF SAID REGENERATED CONTACT CATALYTIC MATERIAL DIRECTLY TO THE CONTACT ZONE, AND RECYCLING THE REMAINDER OF SAID REGENERATED CONTACT CATALYTIC MATERIAL DIRECTLY TO THE FLUID CATALYTIC CRACKING ZONE. 